NITRIDED

COATINGS
Proven materialographic knowledge

APPLICATION NOTE
2 Metallographic preparation of nitrided and nitrocarburized components
METALLOGRAPHIC PREPARATION
OF NITRIDED AND NITRO-
CARBURIZED COMPONENTS
Nitriding is a thermochemical process
by which the surface of a ferrous metal
is enriched with nitrogen to improve the
wear resistance of components. In ni-
trocarburizing, not only nitrogen but also
small amounts of carbon are involved in
the process. The result is a nitrided layer
consisting of the compound layer (“white
layer”) and the diffusion zone immediate-
ly below the compound layer.
The nitriding and nitrocarburizing process
using gas or salt bath was developed in
the early 20th century in Germany and
the United States. The development of ion
or plasma nitriding started in the 1930s
but was not commercially used until the
1970s. All three nitriding methods have
advantages, and the selection of a par-
ticular method depends on the specific
application of the nitrided component.
Nitriding produces a hard, wear-resistant
layer on carbon and low alloy steels and
cast iron. In addition, it considerably
improves fatigue strength and by oxidizing
the nitrided surface, it enhances corrosion
resistance.
The main advantage of nitriding and nitro-
carburizing over other means of surface
Difficulties in the preparation of nitrided parts:
Chipping and cracking in the layer
Fig. 1 Shrinkage gap between specimen 500 x
and mounting resin can cause flaking
of the nitride layer and trap abrasives
hardening is the low process temperature
(500-600°C), preferably 580°C. Com-
ponents can often be nitrided in the fully
hardened and tempered condition with-
out the core properties being adversely
affected. An additional advantage of the
low temperature process is the low risk of
distortion. Consequently, the parts can be
machined to the final dimensions and do
not need costly finishing work after nitrid-
ing, such as grinding or straightening.
Nitriding and nitrocarburizing are mainly
used for ferrous components such as
valves, camshafts and piston rods in the
mechanical engineering and automotive
industries. Other applications are cutting
tools or large forming dies. Cast iron parts,
such as pump and gear houses, can also
be nitrided.
The metallography of nitrided and nitro-
carburized components is mainly used for
controlling the nitriding process through
examination of the layer. The white
layer, diffusion zone and porous zone are Nitrided steel, color etched with
measured and evaluated. In addition, Beraha’s reagent
failure analyses of used parts are carried
out to see if faulty material, surface
deterioration or the nitriding process were
contributing factors.
Edge-rounding
SOLUTION
Plane grinding with SiC paper
Fine grinding with diamond
Diamond polishing on hard cloths
Fig. 2. Without edge retention, the layer
is not in focus at high magnification
 Metallographic preparation of nitrided and nitrocarburized components 3

FORMATION AND
COMPOSITION OF
THE NITRIDED LAYER

At nitriding temperature, the nitrogen

diffuses into the steel surface and reacts

with iron, forming γ’ iron nitride (Fe4N),
containing up to 6 wt % N. With increasing
nitrogen, the ε-phase (Fe3N) is formed,
which can absorb up to 11 wt % N.
These two iron nitride phases, ε+γ’, form
the compound layer, which is also called
“white layer” because it stays white when
the steel is etched with Nital. This com-
pound layer does not contain any metal
but consists of a non-metallic phase
formed by iron and nitrogen that can be
called a “nitride ceramic”. A porous zone
can be found in the outer areas of the
compound layer (see Fig. 3).
The percentage of γ’ and ε-nitride de-
pends on the carbon content of the steel:
a higher carbon content promotes the
formation of ε, whereas a lower carbon
content forms more γ’ iron nitride.
With an optical microscope the differenti-
ation of ε and γ’ iron nitrides in the com-
pound layer is only possible by using very
specialised and difficult etching methods.
A correct analysis of the composition can
only be made by quantitative structural
x-ray analysis using deeply penetrating
radiation.
=18 µm
Compound layer
Enlarged 1000:1
Fig. 3. Details of composition of nitrided layer
Below the compound zone is the diffusion
zone containing nitrogen in solid solution.
In addition, it has stable metal nitrides
formed by the various alloying elements
of the steel, such as aluminum, molybde-
num, chromium and tungsten.
Because of their sub-microscopically fine
distribution, the nitrides in the diffusion
zone of low carbon steels generally
cannot be seen after etching the metal-
lographic sample. However, after heating
the sample to tempering temperature
(200-400°C for 15-30 min), the nitrogen
in solid solution precipitates in the form of
γ’ nitride needles. These nitride needles
{
{ Porous
zone
ε-Nitride
γ ‘-Nitride
• = Fe ° = Possible N-Positions
can be etched so that the diffusion zone
becomes visible and its thickness can
be measured (Fig. 4). On alloy steels the
diffusion zone will be etched dark with
Nital, but the nitrides cannot be resolved
with an optical microscope (Fig. 5).
The thickness of the white layer and the
diffusion zone depends on various param-
eters, of which the most important are
time, temperature and steel composition.
The white layer can be between 0-20 µm
and the diffusion zone up to 0.8 mm,
depending on the requirements of the
application.

The compound layer is relatively hard and

its hardness increases with the increasing
content of nitride- forming alloying
elements, with concurrent reductions
in the case depth. Nitrided carbon steels
have a surface hardness of 300-400 HV
and alloyed steels from 700 HV to more
than 1000 HV.

Fig. 4. Nitrocarburized carbon steel after Fig. 5. Alloyed steel, nitrocarburized

heating for 45 min/300°C, etched with and etched with 1% Nital shows dark
1% Nital showing nitride needles in the diffusion zone and white compound layer
diffusion zone. with dark oxide coat.
4 Metallographic preparation of nitrided and nitrocarburized components
NITRIDING PROCESSES
AND APPLICATION OF
NITRIDED PARTS
Before nitriding, the components have to
be thoroughly cleaned and degreased.
Any surface contamination from grinding
particles, oil or metal chips will result in
an uneven formation of the nitrided layer.
This can cause cracks in the coating,
which leads to flaking and corrosion (see
Figs. 6 and 7). After cleaning, the parts
are dried and preheated and then trans-
ferred to the actual nitriding environment.
The various nitriding processes can be
differentiated mainly by their nitrogen
source and the energy supply. Salt bath,
gas and plasma nitriding have different
advantages regarding investment costs,
process time, environment, safety and
quality. The properties of the resulting
nitrided or nitrocarburized surface are in
many cases independent of the produc-
tion process. The required case depth
is determined by the application of the
nitrided component and can be regulated
through the nitriding temperature and
time.
In the following paragraphs, the different
nitriding processes are briefly described
and the application of the nitrided parts
mentioned.
Salt bath nitrocarburizing
Nitrocarburizing with salt bath is carried
out in gas or electrically-heated crucible
furnaces. The preferred material for the
Fig. 6 and 7. Impurities in the steel and on the surface can lead to faulty areas in
the nitride layer and cause cracking or corrosion.Cuperora
crucible is titanium. After preheating to
350°C, the components are submerged
into the salt bath, either hanging or lying
in charging racks, or as bulk material in
stainless steel or Inconel baskets. The
salt bath consists of alkaline cyanate and
alkaline carbonate. Through oxidation and
thermal reaction with the immersed com-
ponent surface, at nitriding temperature
the alkaline cyanate releases nitrogen and
carbon which diffuse into the surface of
the component. Pure nitriding is not pos-
sible with the salt bath, as small amounts
of carbon will always diffuse into the
surface. The usual process parameters
are 90 min at 580°C.
The active nitrogen-releasing agent of the
salt bath is the alkaline cyanate. Through
the reaction of the cyanate ions, the
amount of alkaline carbonate in the bath
increases. By adding an organic polymer,
the optimal cyanate content of the bath
is replenished again.
After nitrocarburizing, quenching in an
oxidizing salt bath (380-420°C) produces
a black iron oxide (Fe3O4) on the surface.
It fills the pores of the compound layer
and acts as additional corrosion-resistant
protection. After cooling to room
temperature, the components can be
polished and then reoxidized, depending
on the application.
Nitrocarburized cases are particularly
resistant against abrasive wear, scuffing,
sliding friction and corrosion. The porous
surface can retain lubricants, which adds
to the running properties of camshafts,
for example. (Fig. 8)
Salt bath nitrocarburizing is a fast,
flexible and economical process. Typical
applications are parts for the automotive
industry such as piston rods, crank and
camshafts, valves and gears. In addition,
nitrocarburized components are used
in the aircraft and off-shore industries,
and in mechanical engineering.
Gas nitriding and nitrocarburizing gen-
erally takes place in a sealed, bell-type
nitriding furnace which provides good
gas circulation. The process is mainly
controlled by the degree of dissociation
of ammonia. The ammonia gas reacts at
500-520°C with the steel surface and
decomposes, thereby releasing nascent
nitrogen which diffuses into the steel
surface. As gas nitriding uses a lower
temperature, process times are 40-80
hrs. By adding gases containing carbon,
gas nitrocarburizing is also possible (Figs.
9 and 10). As a consequence, process
times are reduced.
The formation and properties of the com-
pound layer and diffusion zone are similar
Fig. 8. Salt bath nitrocarburized alloyed
steel (16MnCr5), etched with 1% Nital.
Diffusion zone is etched dark, compound
layer with porous zone shows white.

NITRIDING PROCESSES
AND APPLICATION OF
NITRIDED PARTS
to those produced by salt bath nitriding.
However, the thickness of the compound
zone can be more accurately controlled
or even completely suppressed with gas
nitriding. This makes the steel surface
very hard but not brittle. Deep diffusion
zones can be produced that have a bene-
ficial effect on mechanical strain caused
by vibration and torsion. Components
with bore holes, undercuts and cavities,
for instance sintered steels, are suited for
gas nitriding because the gas can easily
enter everywhere as it circulates in the
retort. Copper plating or special resistant
materials can be used for masking areas
that should not be nitrided.
Gas nitrided parts are typically machine
spindles, ductile iron pump housings,
door lock mechanisms, water pump com-
ponents and pistons for gas compressors.
Plasma nitriding and nitrocarburizing is
carried out in a nitrogen-hydrogen atmo-
sphere at 400-600°C and a pressure of
approx. 50-500 Pa. For nitrocarburizing,
gases containing carbon are added, such
as methane. The plasma is produced in
a vacuum chamber with a high voltage,
whereby the workpiece acts as cathode
and the vacuum vessel as anode.
Because nitrogen and hydrogen are
brought into the vacuum chamber as
individual gases, the ratio of nitrogen
Fig. 10. Gas nitrocarburized carbon steel,
580°C/1.5 hr.
Metallographic preparation of nitrided and nitrocarburized components 5
to hydrogen can be controlled allowing
variations of thickness and composition
of the compound layer. Consequently,
not only low carbon steels, but also aus-
tenitic steels, powder metallurgy ferrous
metals and refractory metals
can be plasma nitrided.
Plasma nitriding gives a very fine surface
finish, almost free of pores, that lends
itself to a high polish (Fig. 11 and 12).
Due to this low porosity, plasma nitrided
and nitrocarburized cam- and crankshafts
are used for high performance motors, Fig. 9. Alloyed steel (42CrMo4), gas nitrided
for example. As plasma nitriding allows 510°C/36 hrs and etched with 1% Nital
a large variety of nitride layers, its fields showing a dark diffusion zone and white
of application are also varied. Examples compound layer
are the surface treatment of forming
dies, such as large plastic extrusion dies
and auto body blanking dies, tools for
stainless steel deep drawing, casting, hot
forging and extrusion dies. Other specific
applications are corrosion-resistant
engine valves, high-speed steel cutting
tools, and many applications in mechani-
cal engineering.
Fig. 11. Alloyed steel (16MnCr5N), plasma Fig. 12. Carbon steel, plasma
nitrocarburized, 570°C/6 hrs nitrocarburized, 570°C/6 hrs. Both nitride
layers are without a porous zone and have
a very fine surface finish.
6 Metallographic preparation of nitrided and nitrocarburized components

DIFFICULTIES DURING
METALLOGRAPHIC PREPARATION
OF NITRIDED STEELS

The main problem during the preparation
of nitrided components is the chipping
of the porous zone and cracking of the
compound zone (see Figs.1, 2 and 13).
This damage is mostly introduced during
the first grinding step. Incorrect mounting
and long polishing with soft cloths results
in rounded edges. As the evaluation of the
coating is carried out with 1000x magni-
fication, rounded edges lead to incorrect
thickness measurements.
Recommendations for the preparation
of nitrided steels
To avoid damage to the nitride layer, it is
recommended that sectioning is carried
out carefully on a cut-off machine with
water cooling, suitable for metallographic
purposes. For cutting, an aluminum
oxide wheel is selected according to the
hardness of the nitrided component. This
is usually a medium-hard to soft cut-off
wheel.
Mounting: To avoid shrinkage gaps, hot
compression mounting with a fibre rein-
forced resin is recommended (DuroFast).
In addition, wrapping the sectioned
specimen with a thin, pure copper foil
(0.05 mm) before mounting promotes
good edge retention.*
Also, the copper color enhances the con-
trast of the coating against the mounting
resin, which is particularly helpful when
working with oxidized components
(compare Figs. 14 and 15, 16 and 17).

Fig. 13. Cracks in the coating caused
during preparation.
Fig. 14. Alloy steel (16MnCr5N), salt bath
nitrocarburized, mounted without copper
foil. There is flaking of the nitride layer and
the thin oxide layer cannot be distinguished
from the mounting resin.
Fig. 15. Same as Fig.14, mounted with
copper foil; the dark oxide layer is clearly
visible against the copper color of the foil.
The layer is well preserved.

Fig. 16. High alloy steel (X45CrSi9V), salt bath nitrocarburized, oxidized and Fig. 17. Same as Fig.16, mounted with copper foil; the compound
etched with 1% Nital. The diffusion zone is etched dark, and the compound layer can clearly be seen against the copper foil and can be
layer cannot be distinguished from the mounting resin. measured.
 Metallographic preparation of nitrided and nitrocarburized components 7

RECOMMENDED
PREPARATIONS METHOD
FOR NITRIDED STEELS

Grinding and polishing: Plane grinding
is carried out with silicon carbide Foil/
Paper #180 and/or #220. To ensure edge
retention, it is important to fine grind with
diamond on a fine grinding rigid disc
(MD-Largo). This is followed by a diamond
polish on a satin woven acetate cloth
(MD-Dac), and a brief final polish with
1 µm diamond or colloidal silica. The
following method has given good,
reproducible results for nitrided steels.
Depending on the sample size and type
of coating, the polishing times can be
modified slightly.
Etching: The nitrided coating is first
examined unetched to evaluate the
porous zone and the shape and size of
the pores. Etching with 1-3% Nital shows
the white compound layer, and in alloyed
steels, the dark diffusion zone. For a good
nitride case a very good base material is
essential. Cracks, inclusions, banding or
deformation of the initial surface decisive-
ly influence the quality of the nitride layer.
Therefore, it is also important to evaluate
the structure of the base material.
In low carbon steels, the diffusion zone Fig. 18. Ferritic nodular cast iron,
can be identified by heating the sample gas nitrided, etched with 3% Nital.
at 300°C/45 min, and then etching with
1% Nital (see Fig. 4)

Preparation Method for nitrided steels

Grinding Polishing

STEP PG FG DP 1 DP 2 OP*

Surface Foil/Paper MD-Largo MD-Dac MD-Nap MD-Chem

Type SiC Diamond Diamond Diamond Alumina/Silica

Abrasive
Size #220 9 μm 3 μm 1 μm 0.02/0.04 μm
Suspension/ DiaPro OP-A or
Water DiaPro Dac 3 DiaPro Nap B 1
Lubricant Allegro/Largo 9 OP-U NonDry

rpm 300 150 150 150 150

Force [N]/ 25
25 30 25 15
specimen
Removal (μm) 5
As needed 6 1 1
Time (min)
Table 1: Preparation method for samples of nitrided steels, mounted, 30 mm diameter, using the semi-automatic Tegramin, 300 mm diameter.
As an alternative to DiaPro polycrystalline diamond suspension P, 9 μm, 3 μm and 1 μm can be used together with green/blue lubricant.
*Optional step

SUMMARY
Nitriding is a thermochemical process
by which the surface of a ferrous metal
is enriched with nitrogen to improve
the wear and corrosion resistance of
components. Three nitriding methods
can be used: salt bath nitrocarburizing,
nitriding and nitrocarburizing in gas or
plasma. Nitriding and nitrocarburizing
result in the formation of a very hard
surface consisting of the compound layer
and the diffusion zone. The metallography
of nitrided layers is mainly used for quality
control, controlling the nitriding process
and for failure analysis.
The main problems when preparing
nitrided layers are rounded edges and
cracking or chipping of the layer during
grinding and polishing. This problem can
be overcome by carefully wrapping the
sample in a thin copper foil before hot
compression mounting. For fine grinding
silicon carbide, Foil/Paper or diamond on
a fine grinding disc can be used, with the
latter resulting in better edge retention.
The subsequent diamond polishing
should be carried out as long as needed
to remove any damage in the layer intro-
duced by the preparation.
White layer with porous zone on low carbon steel
www.struers.com
28.06.2023 / 62140406
APPLICATION NOTE
Elisabeth Weidmann, Anne Guesnier,
Struers A/S, Copenhagen, Denmark
Acknowledgements
We wish to thank Durferrit GmbH,
Mannheim, Germany, for permission to
reproduce photographs and drawings.
We wish to thank Dr. Ulrich Baudis for his
professional support. We want to especially
thank Ms. Sabine Riesbeck for the sample
preparation and for generously supplying
the color micrograph on page 1 and in
Figs. 2-17.
We wish to thank Eltro GbmH, Baesweiler,
Germany, for supplying plasma nitrided
sample material.
We wish to thank Carl Gommann KG,
Remscheid, Germany, for supplying gas
nitrided sample material.
Bibliography
Practical nitriding and ferritic
mitrocarburizing, David Pye, ASM
International, 2003
ASM Handbook, Vol. 9, Metallography and
Microstructure, ASM, 2004
Wärmebehandlung von Eisenwerkstoffen,
Nitrieren und Nitrocarburieren, D. Liedtke
u.a., expert verlag, Renningen, 2006
Technologie der Salzschmelzen, Ulrich
Baudis und Michael Kreutz, Die Bibliothek
der Technik, Band 224, verlag moderne
industrie, 2001
500x